Process for breaking petroleum emulsions



Fatented Mar. 27, 1945 PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, University City, and Bernhard Kaiser, Webster Groves, Mm,

assignors to Petrolite Corporation, Ltd, Wilmington, DeL, a corporation of Delaware No Drawing. Application .llune 23, 1943, Serial No. 492,184

a Claims. (crass-cs1) This invention relates primarily to the resolution of petroleum emulsions.

One object of our invention is to provide a novel process for resolving petroleum emulsions of the water-in-oil type, that are commonly referred to as cut oil, froily oil," emulsified oil," etc., and which comprises fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitues the continuous phase of the emulsion.

Another object of our invention is to provide an economical and rapid process for separating emulsions which have been prepared under controlled conditions i'rom mineral oil, such as crude of aryl sulfonic acid just described may be referred to as a Twitchell agent, or sulfo-i'atty aromatic acid, or sometimes as a sulfo-aromatic fatty acid, Prior reference to the ester form concerns the carboxyl radical and not the sulfonic acid radical, as is apparent in light of sub-s sequent description. One of the common pro-' cedures employed to manufacture sulioaromatic fatty acids, is to employ a method in which the selected aromatic material and the selected unsaturated fatty acid, such as the oleic acid, are subjected to a sulionation-condensation reaction. Such reaction involves a simultaneous introduction of the fatty acid radical into the aromatic nucleus, along with the simultaneous introduction of one or more sulfonic acid radicals. Thus,

it is our, preferred procedure to manufacture the herein contemplated compounds in the manner thus indicated.

More specifically, the procedure employed is as butadiene oxide, butadiene dioxide, chloroprene oxide, isoprene oxide, decene oxide, styrene oxide, cyclohexylene oxide, cyclopentene oxide, etc. Our

preference is to use an alkylene oxide having not more than four carbon atoms, as, for example, ethylene oxide, propylene oxide, butylene oxide, glycide, or the equivalent.

Although a monocyclic aryl reactant or alcohol may be employed, such as phenylethanol or phenoxyethanol, it is our preference to employ reactants in which there is present a polycyclic aryl nucleus, rather than a monocyclic aryl nucleus. Such hydroxylated aryl compounds, that is, either. the phenol or the aromatic alcohol, or perhaps, more correctly, the aryl alkanol alcohol, was treated with three to ten moles of a suitable oxyalkylating agent, and particularly, one having not over four carbon'atoms; for instance; ethylene oxide, propylene oxide, butylene oxide, or glycide. It is our preference to use an amount of ethylene oxide so that the compound, in ab sence of a; sulfonic acid radical, and in absence of a neutralized carboxyi radical, would not be water-soluble. In other words, we particularly contemplate the type of compound in which the sulfonic acid radical alone, or in combination with the neutralized carboxyl radical, contributes a significant part of the hydrophile property of the finished compound. The simplest manufacturing procedure involves the selection of a suitable aryl material, such as orthophenylphenol, paraphenylphenol, p-tert-amylphenoxy ethanol, di-tert amylphenoxy ethanol, beta- (p-tert butylphenoxy) ethanol, -tert butyl-2-phenylphenol beta-phenoxy ethanol, phenyl ethanol, naphthyl ethanol, phenyl propanol, benzyl alcohol, phenylphenoi, phenylcyclohexanol, as a first step. Such aromatic reactant, that is, the aryl alkanol, or the aryl-oxyalkanol, is treated with approximately 3 to 11 molesof an alkylene oxide, such as ethylene oxide, or propylene oxide. Such procedure is well known. The aryl polyglycol so obtained is subjected to a sulfonation-condensationreaction of the kind previously described, in which anv unsaturated fatty acid is present as a reactantand oleum or the equivalent is used as the sulfonating-and condensing agent. The followin: examples will serve to illustrate such procedure.

- Anrr. Potronrcpr.

I temple 1 Hydroxy di-phenyl is reacted in the customary or with 8 to 10 moles of ethylene oxide, so as toproduce the aryl po ysiyc l'.

the preceding with ethylene oxide in the menu H fOne pound m I ARYL POLYGLYCOL Example 2 One mole of benzyl alcohol is reacted with ethylene oxide in the same manner as in the preceding example.

ARYL PoL'YcLr oor. Example 3 One pound mole of naphthyl ethanol is reacted with ethylene oxide in the manner indicated in Example 1.

Ann. PoLY oLycor.

- 7 Example 4 One pound mole of beta naphthol is reacted er described in Example 1, preceding.

- ARYL POLYGLYCOL Example 5 One pound mole of-4-tert-butyl-2-phenylphenol is treated with ethylene oxide in the same manner as described in Example 1, preceding.

ARYL POLyGLx'coL Example 6 p The same procedure is followed as in Examples l to 5, preceding, except that propylene oxide is substituted for ethylene oxide.

As previously suggested, one class of reactants employed in the production of the herein described sulfo-aromatic fatty acids are higher unsaturated fatty'acids, as exemplified by oleic acid.

\ These unsaturated fatty acids vary in the number of carbon atoms present, from 11 to 22. For

. instance, unsaturated acids having 11 carbon,

SUrroARomrrc CouroUNn -Ea:am'ple1'= w ole of phenylphenol is treated with. ethylene oxide,;as in preceding Aryl polylycol, Example 1, and the oxyalkylated derivative is mixed with one pound mole of oleic acid,

hydrogen-hydrogen sulfate, prepared by reacting one pound mole of oleic acid with ly 'to 2 pound moles of sulfuric monohydrate and immediately employing the mixture thus obtained.

One-to two pound moles of sulfuric acid 96% or weak oleum are added. The mass is stirred constantly at a temperature which precludes the formation of any significant amount of sulfur dioxide. A temperature of 35-55 C. is particu-. larly suitable, and the mass may be stirred for approximately 3-10 hours, until tests indicate "that both the'sulfonation reaction and the condensation reaction are complete. A reaction temperature as high as -'75 (Lean be employed,

if need be. The sulfonated mass is then diluted with water until it shows a tendency to separate readily. It is then permitted to remain in quiescent state, until such separation is complete. The lower layer of dilute acid is withdrawn. The acidic mass is neutralized with a suitable base so as to convert the sulfonic acid radical atom is permitted to remain unneutralized. Generally speaking, this means neutralization to themethyl orange end point. Any suitable base may be employed. Such basic materials include caustic soda, caustic potash, ammonium hydrate, triethanolamjne, oxyethylated triethanolamine. derived by treating triethanolamine with ethylene' oxide and oxyethylated tris(hydroxymethyDaminomethane, derived by treatment of tris(hydroxymethyl)aminomethane with ethylene oxide. These bases enhance water solubllty.

SULFOAROMATIC COMPOUND Example 2 "One pound mole of 4-tert butyl- 2-phenylphenol is substituted for one pound mole of hydroxy phenylphenol in Example 1, preceding.

SULFoARoMA'rrc COMPOUND Example '3 One pound mole of the naphthyl polyglycol obtained as aryl polyglycol, Example 3, preced- 0 phenol.

SULFoARoMA'rrc QOMPOUND Example 4 Hydroxy phenylphenol (diphenylol), is substitnted for phenylphenol in Example 1, preceding. The amount of ethylene oxide employed is doubled, due to the presence of the two reactive hydroxyl radicals;

SULFOAROMATIC COMPOUND Example 5 The same procedure is followed as in Examples 1 to 4, preceding, except that undecylenic acid isjsubstituted for oleic acid in the preceding Examples-1 to 4, inclusive.

SULFOAROMATIC COMPOUND Example 6 The same procedure is employed as in Examples 1 to 4, preceding, except that erucic acid is substituted for oleic acid.

SULFOAROMATIC COMPOUND Example 7 The same procedure is followed as in Examples 1 to 4, preceding, except that the mixed fatty acids derived from sunflower seed oil or teaseed oil is used instead of oleic acid.

I sunrosaomarrc COMPOUND Example 8 The same procedure is followed as in Examples 3 '1 to 'l, preceding, except that the acidic mass is employed as such, or after neutralization with a base which tends to reduce water solubility, and in fact, may result in a compound which is. either oil-soluble, or almost water-insoluble, or completely water-insoluble, or may show extreme insolubility in either watero'r oil. Among the suitable bases for such purposes are: Pyridine, cyclohexylamine', dicyclohexylamine, ben zylamine.

into the salt form. The carboxylic hydrogen ing, is substituted for one pound mole of phenyl dibenzylamine, amylam'ine, diamylamine, trl-' amylamine, octadecylamine, and particula ly' high'molal amines, which, in the form of the acetate, show surface activity.

SULFOAROMATIC COMPOUND Example 9 tive, i. e., quaternary bases of the kind that the chloride, nitrite, bromid, acetate, lactate, and

the like, show surface-activity in aqueous sol- 1 ution. Generally speaking, such quaternary compounds are more apt to be available in the form of salts, for instance, a chloride or bromide,- rather than in the form of the free base. In the light of this fact, salts of the kind herein contemplated, i. e., sulfonates, are best obtained metathetically. The two conventional procedures for such metathetical reactions involve preparing the sodium, potassium, the ammonium salt of the sulfonic acids previously described, and then reacting an alcoholic solution of such salts with an alcohol solution of the quaternary chloride or bromide. Another procedure involves the principle that the combination of a surfaceactive anion and surface-active cation is apt to produce a salt which is insoluble in water, in the absence of [an excess of either reactant. Thus, an aqueous solution of the sodium, potassium, or ammonium salt of the kind described in the preceding examples may be reacted in dilute solution, for instance, with a 5% solution of cetyl pyridinium bromide, or any one of a number of other surface-active quaternary halides, as, for example, those described in our .co-pending application Serial No. 463,439, filed October 26, 1942.

Incidentally, in the various examples, the carboxyl radical may be converted into the salt form by neutralization with any of the indicated bases.

Previous reference has been made to the fact that the carboigvl radical may be converted from the free acid form into salt or an ester. When converted into an ester, the carbon radical which replaces the ionizable hydrogen atom may be derived from an aliphatic alcohol, an alicyclic alcohol, or an aryl allsyl alcohol. Thus, before. washing the acidic mass, one may add a suitable alcohol, and particularly, a low molal aliphatic alcohol, such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, octyl alcohol, decyl alcohol, or even a high molal alcohol, such as hexadecyl alcohol, octadecyl alcohol, etc., or any-isomer thereof, and permit esteriiication to take place by reaction with the carboxyl radical. The sulfuric acid or oleum used as a .sulfonation-condensation agent, also acts as an SULFoARoMA'rIc COMPOUND Example p The same procedure is followed. as in the premethane.

0 acid, 96% strength, is added in amounts equivalent to 3 moles of sulfuric acid for each mole of alcohol added. The alcohols added are anhydrous, or preferably, substantially anhydrous. The acidicmass so obtained is permitted to stand for approximately 3 to 10 days at approximately 20-35 C., until the esterification reaction is substantially complete, as indicated by substantial disappearance of free carboxyl radicals. The acidic mass is then separated in the conventional manner previously described, and the sulfonic acid radical and any residual carboxyl radical present are neutralized by means of any one of the bases previously indicated, which may be of the type that enhance water solubility. The excess of low molal alcohol present is permitted to remain or be removed by distillation.

It is to be noted that in the polycyclic aryl compounds described, that one may employ either the condensed polycyclic type or the isolated type. We do not, however, contemplate the type of compound obtained from a reactant'in which the aryl nuclei are separated by a non-aryl carbon atom, as, for example, in diphenylol dimethyl In light of what has been said, numerous other means or procedures may be employed for manufacturin the compounds herein contemplated. For instance, one can obtain hydroxyaryl fatty acids which can be subjected to Oxyalkylation and then sulfonated. Various pro cedures can be employed for obtaining sulfoaromatic fatty acids. Oxyalkylation may involve the sulfonic acid radical so that the sulfonic acid is converted into a glycol or polyglycol ester having a residual hydroxyl radical. Reference is made to the following patents which are concerned with the production of sulfoaromatic fatty acids or compounds which can be readily converted into the same by sulfonation: U. 8. Patents Nos. 1,642,595, dated Sept. 13, 1927; 1,779,- 345, dated Oct. 21, 1930'; and 2,302,070, dated Nov. 17, 1942; British Patents Nos. 286,796, dated Mar. 13, 1928; and 454,183, dated Sept. 25, 1936; German Patents Nos. 492,508, dated Feb. 6, 1930; 538,762, dated Nov. 5, 1931; 589,508, dated Nov. 23, 1933; 663,983, dated July 28, 1938; and 678,134, dated July 8, 1939.

Summarizing what has been said, the type of aryl polyglycol sulfonic acid contemplated herein may be exemplified by the following formula:

in which R1 is an aryl radical,

'i'atty acid, R3=R2COOH, and R4 is a member of the class of aliphatic hydrocarbon radicals,

- alicyclic hydrogen radicals, arylalkyl hydrocarthe. numeral -zer o, one or two, with the proviso that there must be at least one occurrence of a l'lz-lh-COO is the fatty acid residue of the unsaturated fatty acid In the reaction of the kind noted, the double bond of the fatty acid radical becomes saturated by the introduction of the aromatic nucleus, and

the nuclear hydrogen atom- Actually, it isimmaterial whether the nuclear hydrogen atom attaches itself to radical R2 and the aryl radical to R3, or inversely, the hydrogen atom to R3 and the aryl radical to R2. One form is simply the metamer of the other form. Any isomeric or metameric form is equally satisfactory. It is understood that the formulas in the hereto appended claims include all isomeric, and particularly, all metameric forms. An ordinary oleic acid ethylene linkage appears at the 9-10 carbon atom position. -With other unsaturated acids-the position might vary. The formula bringsout clearly the fact that the fatty acid radical is nuclearly linked, so as to present a branch chain arrangement.

Conventional demulsiiying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water; petroleum hydrocarbons, such as gasoline, kerosene, stove oil; a coal tar product, such as benzene, toluene, xylene, tar acid oil, cresol', anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diliients. Sinailariy, the material or materialsemployed as the demulsifying agent of our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials'may be used alone, or in admixture with other suitable well known classes of demulsifying agents. 4

.It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oil and water solubility. Sometimes, they may be used in a form which exhibits relatively limited oil solubility. .However, since such reagents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to 30,000, such an the reagent or demulsifying agent contemplated in our process is based upon its ability to treat certain emulsions more advantageously and at a somewhat lower cost than is possible with other available demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsiiying agent or treating agent herein described will find comparatively limited application, so far as the majority of oil field emulsions are concerned, but we have found that such a demulsifying agent has commercial value, as it will. economically break or resolve .oi l field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the demulsi fying agents heretofore available.

In practising our process for resolving petroleum emulsions of the water-in-oil type, a treating agent or demulsifying agent oi! the kind above described is brought into contact with or caused to act uponthe emulsion to be treated, in any of the various ways, or by any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone, or in combination with other 'demulsifying procedure,

' such as the electrical dehydration process.

The demulsifier herein contemplated may be employed in connection with what is commonly known as down-the-hole procedure, 1. e., bringing the demulsifler in contact with the fluids oi the well at the bottom of the well, or at some point prior to the emergence of said well fluids. This particular type of application is decidedly feasible when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

The chemical products or compounds herein described constitute the subject-matter or our divisional application Serial No. 530,046, filed April 7, 1944.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

l. A process for breaking petroleum emulsions of the water-in-oil type, which consists in sub- ,iecting the emulsion to the action of a demulsifier comprising an aryl polyglycol sulfonate of in which R1 is an aryl radical,

shampo- ,is the fatty acid residue of the unsaturated higher fatty acid, R3=R2COOH, and R4 is a member of the class consisting of aliphatic hydrocarbon radicals, and cations including hydrogen; M is a cation including hydrogen; 1:. is a small whole number greater than one and not in excess of ten; m is a small whole number varying from 3 to 11, and m represents the numeral zero, one or two, with the proviso that there must be at least one occurrence of a'polyglycol radical containing at least 4 oxygen atoms, including the hydroxyl oxygen atom.

2. A process for breaking petroleum emulsions, of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifier comprising an aryl polyglycol sulfonate or the formula; s

soiM N) run g [C..H:O(C..H:..0)..H]..' in which R1 is a polycyclic aryl radical,

is t e fatty acid residue of the unsaturated higher fat acid, R3=R2COOH, and R4 is a member of the class consisting of aliphatic hydrocarbon radicals and cations including hydrogen; M is a cation including hydrogen; n is a small whole number greater than one and not in excess of in which R1 is a polycyclic aryl radical in which the nuclei are isolated,

l ial iz( (Ni-- is the fatty acid residue of the unsaturated higher fatty c and R4 is a member of the class consisting of aliphatic hydrocarbon radicals and cations including hydrogen; M is a cation including hydrogen; n is a-small whole a number greater than one and not in excess or ten; m is a small whole number varying from 3 to 11, and m represents the numeral zero, one or two, with the proviso that there must be at least one occurrence of a polyglycol radical containing at least 4 oxygen atoms, including the hydroxyl oxygen atom.

4. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifier comprising an aryl polyglycol sulfonate of the formula:

' som in which R1 is a polycyclic aryl radical in which the nuclei are isolated,

l hl 'i2(f0 is the fatty acid residue of the unsaturated 18 carbon atom fatty acid, R3 'COOH, and R4 is a member of the class consisting of aliphatic hydrocarbon radicals and cations including hydrogen: M is a cation including hydrogen; n is a small whole number greater than one and not in excess of ten; m is a small whole number varying from 3 to 11, and m represents the numeral zero, one or two, with the proviso that there must be at least one occurrence of a polyglycol radical containing at least 4 oxygen atoms. including the hydroxyl oxygen atom.

5. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjectingjhe emulsion to the action of ademulsifier comprising an aryl polyglycol sulfonate of the formula:

in which R1 is a polycyclic aryl radical in which the nuclei are isolated,

is the fatty acid residue of the unsaturated 18 carbon atom fatty acid, R3=R2COOH, and R4 is a member of the class consisting of aliphatic hydrocarbon radicals and cations including hydrogen; M is a cation including hydrogen; m is a small whole number varying from 3 to 11, and m represents the numeral zero, one or two, with the proviso that there must be at least one occurrence of a polyglycol radical containing'at least 4 oxygen atoms including the hydroxyl oxygen atom. 6. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifier comprising an aryl polyglycol sulfonate of the formula:

in which R1 is a polycyclic aryl radical in which the nuclei are isolated,

I I R1RC-OO- is the fatty acid residue of the unsaturated 18 carbon atom 'fatty acid, R3=RzCOOH, and R4 in which R1 is a. polycyclic aryl radical in which the nuclei are isolated,

I ZI ICOO is the fatty acid residue of the unsaturated 18 carbon atom fatty acid, R3=R2COOH, and R4 is a member of the class consisting of aliphatic hydrocarbon radicals and cations including hydrogen; M isa cation including hydrogen; and m is a small whole number varying from 6 to 8.

8. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifier comprising an aryl polyglycol sulfonate of the formula:

so=M H.113 lJ- R4000. 1

o c1m0)..m

in which R1 is a polycyclic aryl radical in which the nuclei are isolated,

is the fatty acid residue of the unsaturated 18 

